Tetra­aqua­bis­{5-[4-(imidazol-1-yl-κN3)phen­yl]tetra­zolido}manganese(II)

Cheng, X.-C.

doi:10.1107/S1600536811047428

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1757

https://doi.org/10.1107/S1600536811047428

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Tetraaquabis{5-[4-(imidazol-1-yl-κN³)phenyl]tetrazolido}manganese(II)

Xiao-Chun Cheng ^a ^*

^aFaculty of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaian 223003, People's Republic of China
^*Correspondence e-mail: shxycheng@163.com

(Received 4 November 2011; accepted 9 November 2011; online 12 November 2011)

In the title complex, [Mn(C₁₀H₇N₆)₂(H₂O)₄], the Mn²⁺ cation is located on a twofold rotation axis and is coordinated by two N atoms from two 5-[4-(imidazol-1-yl)phenyl]tetrazolide ligands and four O atoms from four water molecules, displaying a distorted MnN₂O₄ octahedral geometry. The crystal structure is stabilized by intermolecular O—H⋯N hydrogen bonds involving the coordinated water molecules and the N atoms of the tetrazolide group.

Related literature

For related structures, see: Huang et al. (2009 ).

Experimental

Crystal data

[Mn(C₁₀H₇N₆)₂(H₂O)₄]
M_r = 549.44
Triclinic, $[P \overline 1]$
a = 8.415 (3) Å
b = 8.458 (3) Å
c = 8.722 (3) Å
α = 80.758 (5)°
β = 75.880 (4)°
γ = 88.791 (5)°
V = 594.1 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.888, T_max = 0.888
3143 measured reflections
2198 independent reflections
2027 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.07
2198 reflections
169 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2W⋯N5ⁱ	0.85	2.00	2.796 (2)	155
O2—H2WA⋯N6ⁱⁱ	0.82	2.05	2.844 (2)	161
O1—H1W⋯N4ⁱ	0.92	1.93	2.819 (2)	163
O1—H1WA⋯N3ⁱⁱⁱ	0.85	1.92	2.769 (2)	175
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y-1, z; (iii) x, y-1, z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811047428/pv2481sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047428/pv2481Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047428/pv2481Isup4.cdx

checkCIF report

Comment top

Multidentate ligand, 1-(5-tetrazolyl)-4-(imidazol-1-yl)benzene, may be used to synthesize complexes for its variable coordination modes. Herein, we report the crystal structure of the title complex wherein the Mn ion is located on a two fold rotation axis and is coordinated by two N atoms from two ligand molecules and four O atoms from four coordinated water molecules, displaying a distorted MnN₂O₄ octahedral geometry (Fig. 1). The ligand displays a monodentate coordinating mode and acts as counteranion due to the deprotonation of tetrazolyl group. In the crystal structure, there exist O—H···N hydrogen bonds (Table 1). Coordinated water molecules and N atoms of tetrazolyl group as donor or acceptor play very important role in the formation of these hydrogen bonds and stabilize the crystal structure.

Related literature top

For related structures, see: Huang et al. (2009).

Experimental top

Reaction mixture of manganese perchlorate hexahydrate (72.3 mg, 0.2 mmol), 1-(5-tetrazolyl)-4-(imidazol-1-yl)benzene (21.2 mg, 0.1 mmol), and potassium hydroxide (5.61 mg, 0.1 mmol) in 12 ml H₂O was sealed in a 16 ml Teflon-lined stainless steel container and heated to 393 K for 3 days. After cooling the stainless steel container to the room temperature, colorless block crystals of the title complex were obtained.

Structure description top

For related structures, see: Huang et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. : The coordination environment of manganese ion in the title complex with the ellipsoids drawn at the 30% probability level. The hydrogen atoms have been omitted for clarity. Symmetry code: A = -x + 2, -y, -z+2.

Tetraaquabis{5-[4-(imidazol-1-yl-κN³)phenyl]tetrazolido}manganese(II) top

Crystal data top

[Mn(C₁₀H₇N₆)₂(H₂O)₄]	Z = 1
M_r = 549.44	F(000) = 283
Triclinic, P1	D_x = 1.536 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.415 (3) Å	Cell parameters from 2041 reflections
b = 8.458 (3) Å	θ = 2.4–28.3°
c = 8.722 (3) Å	µ = 0.61 mm⁻¹
α = 80.758 (5)°	T = 293 K
β = 75.880 (4)°	Block, colorless
γ = 88.791 (5)°	0.20 × 0.20 × 0.20 mm
V = 594.1 (4) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	2198 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
φ and ω scans	θ_max = 25.6°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.888, T_max = 0.888	k = −5→10
3143 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0442P)² + 0.2267P] where P = (F_o² + 2F_c²)/3
2198 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mn(C₁₀H₇N₆)₂(H₂O)₄]	γ = 88.791 (5)°
M_r = 549.44	V = 594.1 (4) Å³
Triclinic, P1	Z = 1
a = 8.415 (3) Å	Mo Kα radiation
b = 8.458 (3) Å	µ = 0.61 mm⁻¹
c = 8.722 (3) Å	T = 293 K
α = 80.758 (5)°	0.20 × 0.20 × 0.20 mm
β = 75.880 (4)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2198 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2027 reflections with I > 2σ(I)
T_min = 0.888, T_max = 0.888	R_int = 0.014
3143 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
2198 reflections	Δρ_min = −0.30 e Å⁻³
169 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7451 (2)	0.5606 (2)	0.7075 (2)	0.0361 (4)
C2	0.8080 (3)	0.6654 (3)	0.5691 (3)	0.0486 (5)
H2	0.9208	0.6794	0.5304	0.058*
C3	0.7036 (2)	0.7498 (3)	0.4877 (3)	0.0443 (5)
H3	0.7472	0.8196	0.3934	0.053*
C4	0.5364 (2)	0.7327 (2)	0.5431 (2)	0.0324 (4)
C5	0.4748 (3)	0.6291 (3)	0.6838 (3)	0.0557 (6)
H5	0.3620	0.6169	0.7239	0.067*
C6	0.5787 (3)	0.5430 (3)	0.7659 (3)	0.0550 (6)
H6	0.5357	0.4734	0.8605	0.066*
C7	0.4287 (2)	0.8208 (2)	0.4509 (2)	0.0310 (4)
C8	0.8260 (3)	0.3192 (2)	0.8712 (2)	0.0396 (4)
H8	0.7257	0.2651	0.8954	0.048*
C9	1.0742 (3)	0.3767 (3)	0.8576 (3)	0.0541 (6)
H9	1.1804	0.3691	0.8713	0.065*
C10	1.0145 (3)	0.5054 (3)	0.7786 (3)	0.0583 (7)
H10	1.0707	0.6004	0.7280	0.070*
Mn1	1.0000	0.0000	1.0000	0.02857 (14)
N1	0.9560 (2)	0.25905 (19)	0.9145 (2)	0.0393 (4)
N2	0.8541 (2)	0.46819 (19)	0.7876 (2)	0.0382 (4)
N3	0.48043 (19)	0.8941 (2)	0.29971 (18)	0.0366 (4)
N4	0.3458 (2)	0.9572 (2)	0.25971 (18)	0.0392 (4)
N5	0.21984 (19)	0.9230 (2)	0.38155 (19)	0.0413 (4)
N6	0.26763 (19)	0.8368 (2)	0.50521 (18)	0.0386 (4)
O1	0.74178 (16)	−0.05589 (19)	1.03254 (16)	0.0461 (4)
H1WA	0.6635	−0.0665	1.1168	0.055*
H1W	0.6996	−0.0410	0.9438	0.055*
O2	1.03428 (16)	−0.04640 (18)	0.75458 (15)	0.0415 (3)
H2W	0.9801	−0.0074	0.6872	0.050*
H2WA	1.1108	−0.0900	0.6996	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0377 (10)	0.0331 (10)	0.0391 (11)	0.0082 (8)	−0.0168 (8)	0.0006 (8)
C2	0.0297 (10)	0.0528 (13)	0.0558 (14)	0.0005 (9)	−0.0126 (9)	0.0164 (10)
C3	0.0347 (10)	0.0464 (12)	0.0438 (12)	−0.0013 (9)	−0.0098 (9)	0.0166 (9)
C4	0.0314 (9)	0.0353 (9)	0.0294 (9)	0.0071 (7)	−0.0086 (7)	−0.0006 (7)
C5	0.0304 (11)	0.0787 (17)	0.0436 (12)	0.0086 (10)	−0.0024 (9)	0.0214 (11)
C6	0.0427 (12)	0.0678 (15)	0.0411 (12)	0.0094 (11)	−0.0057 (10)	0.0229 (11)
C7	0.0281 (9)	0.0377 (9)	0.0259 (9)	0.0050 (7)	−0.0064 (7)	−0.0018 (7)
C8	0.0394 (10)	0.0348 (10)	0.0434 (11)	0.0055 (8)	−0.0155 (9)	0.0049 (8)
C9	0.0471 (13)	0.0433 (12)	0.0767 (17)	0.0004 (10)	−0.0358 (12)	0.0085 (11)
C10	0.0505 (13)	0.0410 (12)	0.0866 (19)	−0.0056 (10)	−0.0392 (13)	0.0158 (12)
Mn1	0.0232 (2)	0.0344 (2)	0.0247 (2)	0.00559 (15)	−0.00588 (15)	0.00465 (15)
N1	0.0427 (9)	0.0342 (8)	0.0419 (9)	0.0069 (7)	−0.0179 (8)	0.0015 (7)
N2	0.0398 (9)	0.0337 (8)	0.0434 (9)	0.0063 (7)	−0.0202 (8)	0.0022 (7)
N3	0.0278 (8)	0.0523 (10)	0.0270 (8)	0.0062 (7)	−0.0069 (6)	0.0015 (7)
N4	0.0318 (8)	0.0579 (11)	0.0259 (8)	0.0081 (7)	−0.0097 (7)	0.0019 (7)
N5	0.0303 (8)	0.0630 (11)	0.0277 (8)	0.0126 (8)	−0.0077 (7)	0.0008 (8)
N6	0.0294 (8)	0.0560 (10)	0.0268 (8)	0.0117 (7)	−0.0060 (6)	0.0015 (7)
O1	0.0231 (6)	0.0790 (11)	0.0296 (7)	0.0009 (6)	−0.0052 (5)	0.0090 (7)
O2	0.0329 (7)	0.0649 (9)	0.0247 (7)	0.0167 (6)	−0.0066 (5)	−0.0037 (6)

Geometric parameters (Å, º) top

C1—C6	1.371 (3)	C9—N1	1.367 (3)
C1—C2	1.374 (3)	C9—H9	0.9300
C1—N2	1.431 (2)	C10—N2	1.373 (3)
C2—C3	1.379 (3)	C10—H10	0.9300
C2—H2	0.9300	Mn1—O1	2.1737 (15)
C3—C4	1.374 (3)	Mn1—O1ⁱ	2.1737 (15)
C3—H3	0.9300	Mn1—O2	2.1870 (15)
C4—C5	1.381 (3)	Mn1—O2ⁱ	2.1870 (15)
C4—C7	1.469 (2)	Mn1—N1	2.2514 (17)
C5—C6	1.385 (3)	Mn1—N1ⁱ	2.2514 (17)
C5—H5	0.9300	N3—N4	1.340 (2)
C6—H6	0.9300	N4—N5	1.305 (2)
C7—N6	1.334 (2)	N5—N6	1.343 (2)
C7—N3	1.334 (2)	O1—H1WA	0.8528
C8—N1	1.310 (2)	O1—H1W	0.9171
C8—N2	1.345 (3)	O2—H2W	0.8511
C8—H8	0.9300	O2—H2WA	0.8226
C9—C10	1.348 (3)

C6—C1—C2	119.82 (18)	O1—Mn1—O2	86.80 (5)
C6—C1—N2	120.54 (18)	O1ⁱ—Mn1—O2	93.20 (5)
C2—C1—N2	119.62 (18)	O1—Mn1—O2ⁱ	93.20 (5)
C1—C2—C3	119.91 (19)	O1ⁱ—Mn1—O2ⁱ	86.80 (5)
C1—C2—H2	120.0	O2—Mn1—O2ⁱ	180.0
C3—C2—H2	120.0	O1—Mn1—N1	90.17 (6)
C4—C3—C2	121.27 (19)	O1ⁱ—Mn1—N1	89.83 (6)
C4—C3—H3	119.4	O2—Mn1—N1	89.07 (6)
C2—C3—H3	119.4	O2ⁱ—Mn1—N1	90.93 (6)
C3—C4—C5	118.23 (18)	O1—Mn1—N1ⁱ	89.83 (6)
C3—C4—C7	119.87 (17)	O1ⁱ—Mn1—N1ⁱ	90.17 (6)
C5—C4—C7	121.88 (17)	O2—Mn1—N1ⁱ	90.93 (6)
C4—C5—C6	120.9 (2)	O2ⁱ—Mn1—N1ⁱ	89.07 (6)
C4—C5—H5	119.5	N1—Mn1—N1ⁱ	180.0
C6—C5—H5	119.5	C8—N1—C9	105.09 (17)
C1—C6—C5	119.8 (2)	C8—N1—Mn1	127.28 (14)
C1—C6—H6	120.1	C9—N1—Mn1	125.60 (14)
C5—C6—H6	120.1	C8—N2—C10	106.15 (16)
N6—C7—N3	111.17 (16)	C8—N2—C1	126.58 (17)
N6—C7—C4	125.02 (17)	C10—N2—C1	126.85 (17)
N3—C7—C4	123.81 (16)	C7—N3—N4	105.15 (15)
N1—C8—N2	112.29 (19)	N5—N4—N3	109.18 (15)
N1—C8—H8	123.9	N4—N5—N6	109.87 (15)
N2—C8—H8	123.9	C7—N6—N5	104.64 (15)
C10—C9—N1	110.2 (2)	Mn1—O1—H1WA	130.2
C10—C9—H9	124.9	Mn1—O1—H1W	118.1
N1—C9—H9	124.9	H1WA—O1—H1W	109.5
C9—C10—N2	106.3 (2)	Mn1—O2—H2W	127.1
C9—C10—H10	126.8	Mn1—O2—H2WA	129.2
N2—C10—H10	126.8	H2W—O2—H2WA	102.8
O1—Mn1—O1ⁱ	180.0

C6—C1—C2—C3	−1.4 (4)	O2ⁱ—Mn1—N1—C8	−107.15 (18)
N2—C1—C2—C3	177.3 (2)	N1ⁱ—Mn1—N1—C8	144 (100)
C1—C2—C3—C4	0.7 (4)	O1—Mn1—N1—C9	−175.28 (19)
C2—C3—C4—C5	0.4 (3)	O1ⁱ—Mn1—N1—C9	4.72 (19)
C2—C3—C4—C7	−178.2 (2)	O2—Mn1—N1—C9	−88.48 (19)
C3—C4—C5—C6	−0.8 (4)	O2ⁱ—Mn1—N1—C9	91.52 (19)
C7—C4—C5—C6	177.7 (2)	N1ⁱ—Mn1—N1—C9	−17 (100)
C2—C1—C6—C5	1.0 (4)	N1—C8—N2—C10	−0.5 (3)
N2—C1—C6—C5	−177.7 (2)	N1—C8—N2—C1	172.43 (18)
C4—C5—C6—C1	0.1 (4)	C9—C10—N2—C8	−0.1 (3)
C3—C4—C7—N6	−167.3 (2)	C9—C10—N2—C1	−173.0 (2)
C5—C4—C7—N6	14.2 (3)	C6—C1—N2—C8	31.4 (3)
C3—C4—C7—N3	13.6 (3)	C2—C1—N2—C8	−147.2 (2)
C5—C4—C7—N3	−164.9 (2)	C6—C1—N2—C10	−157.1 (2)
N1—C9—C10—N2	0.6 (3)	C2—C1—N2—C10	24.2 (3)
N2—C8—N1—C9	0.8 (3)	N6—C7—N3—N4	−0.1 (2)
N2—C8—N1—Mn1	−163.53 (14)	C4—C7—N3—N4	179.14 (17)
C10—C9—N1—C8	−0.9 (3)	C7—N3—N4—N5	0.0 (2)
C10—C9—N1—Mn1	163.81 (18)	N3—N4—N5—N6	0.1 (2)
O1—Mn1—N1—C8	−13.94 (18)	N3—C7—N6—N5	0.2 (2)
O1ⁱ—Mn1—N1—C8	166.06 (18)	C4—C7—N6—N5	−179.05 (18)
O2—Mn1—N1—C8	72.85 (18)	N4—N5—N6—C7	−0.2 (2)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2W···N5ⁱⁱ	0.85	2.00	2.796 (2)	155
O2—H2WA···N6ⁱⁱⁱ	0.82	2.05	2.844 (2)	161
O1—H1W···N4ⁱⁱ	0.92	1.93	2.819 (2)	163
O1—H1WA···N3^iv	0.85	1.92	2.769 (2)	175

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z; (iv) x, y−1, z+1.

Experimental details

Crystal data
Chemical formula	[Mn(C₁₀H₇N₆)₂(H₂O)₄]
M_r	549.44
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.415 (3), 8.458 (3), 8.722 (3)
α, β, γ (°)	80.758 (5), 75.880 (4), 88.791 (5)
V (Å³)	594.1 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.888, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	3143, 2198, 2027
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.07
No. of reflections	2198
No. of parameters	169
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.30

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2W···N5ⁱ	0.85	2.00	2.796 (2)	155.2
O2—H2WA···N6ⁱⁱ	0.82	2.05	2.844 (2)	161.4
O1—H1W···N4ⁱ	0.92	1.93	2.819 (2)	163.4
O1—H1WA···N3ⁱⁱⁱ	0.85	1.92	2.769 (2)	174.9

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y−1, z; (iii) x, y−1, z+1.

References

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